EP1161516A1 - Sulfoniertes copolymer und verfahren zur reinigung von oberflächen und/oder zur herstellung von flecken abweisenden eigenschaften dieser oberflächen und/oder zur entfernung von flecken oder verschmutzungen - Google Patents

Sulfoniertes copolymer und verfahren zur reinigung von oberflächen und/oder zur herstellung von flecken abweisenden eigenschaften dieser oberflächen und/oder zur entfernung von flecken oder verschmutzungen

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Publication number
EP1161516A1
EP1161516A1 EP00910901A EP00910901A EP1161516A1 EP 1161516 A1 EP1161516 A1 EP 1161516A1 EP 00910901 A EP00910901 A EP 00910901A EP 00910901 A EP00910901 A EP 00910901A EP 1161516 A1 EP1161516 A1 EP 1161516A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
units
sulfonated
polyamide
aliphatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00910901A
Other languages
English (en)
French (fr)
Other versions
EP1161516B1 (de
Inventor
Simon Firkins
Marie-Eve Perier
Sandrine Rochat
Louis Vovelle
Gladys Saliba Gabriel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
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Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1161516A1 publication Critical patent/EP1161516A1/de
Application granted granted Critical
Publication of EP1161516B1 publication Critical patent/EP1161516B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C11D2111/14—

Definitions

  • the subject of the present invention is a new sulfonated copolymer comprising polyether and polyamide units, its process of preparation and its use as a detergent agent for hard or textile surfaces, in particular in synthetic polymer, very particularly in textile surfaces in polyamide, and / or as agent capable of providing said surfaces with stain resistance properties and / or making it possible to facilitate the removal of stains and soil release from said surfaces. It also relates to a process implementing said sulfonated copolymer, for cleaning and / or treating said surfaces in order to provide them with stain resistance properties (stain resistance) and / or making it possible to facilitate the removal of stains and soil release. It further relates to detergent compositions comprising said copolymer.
  • Patent application WO92 / 02570 describes dyed articles (fibers, carpets) of polyamide, resistant to acid stains, said polyamide being a polyhexamethyiene adipamide, a poly- ⁇ -caprolactam or a hexamethylene diamine / adipic acid / - ⁇ -caprolactam copolymer , containing from 1 to 4% by weight of sulfonated aromatic carboxylic groups (for example 5-isophthalic acid) and having from 20 to 40 milliequivalent amino terminations for 10 6 g, said polyamide being dyed using an acid dye.
  • sulfonated aromatic carboxylic groups for example 5-isophthalic acid
  • French patent application FR-A-2 722 804 describes water-soluble and / or water-dispersible copolyamides with a molecular mass of 2,000 to 30,000, comprising aromatic and / or aliphatic dicarbonyl units, sulfoaryldicarbonyl units and polyoxyalkylene-diamine units, alone or with aliphatic diamine patterns, and their use for sizing ("size") synthetic polyamide threads or synthetic polyamide fibers optionally mixed with natural, artificial or other synthetic fibers.
  • a first subject of the invention consists of a water-soluble or water-dispersible copolymer (C) comprising
  • said polvoxyalkylene unit (POA) comprises from 2 to 200, preferably from 5 to 150 similar or different oxyalkylene units, the linear or branched alkylene residue of which contains from 2 to 12, preferably from 2 to 6 carbon atoms, very particularly 2 or 3 carbon atoms - said sulfonated polyamide unit (PAS) comprises,
  • A represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group.
  • D represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group optionally interrupted by one or more heteroatoms of oxygen or tertiary nitrogen
  • K represents an aliphatic, cycloaliphatic or aromatic group.
  • R are identical or different and represent a hydrogen atom or a C1-C4 alkyl group (ii) of similar or different sulfonated functional units (mS) of formula
  • the symbol Q represents an aromatic, aliphatic or cycloaliphatic hydrocarbon group
  • L is a valence bond or an alkylene, alkoxyalkylene, oxyalkylene, arylene, alkylarylene, alkoxyarylene group
  • n is greater than or equal to 1 (iii) and binding groups ( ⁇ lPAS) of the units of said sulfonated polyamide unit (PAS ⁇
  • R similar or different, represents a hydrogen atom or a C-1-C4 alkyl group
  • the rate of SO3M functions, expressed in mass of SO3 " function, in said unit (s) (PAS) is such that it represents at least 0.1%, preferably at least 0.2%, very particularly at least 0 , 4%, in particular from 0.4 to 15% of the total mass of copolymer (C) * the mass ratio of all of the units (POA) / mass of all of the units (PAS) is 95/5 to 30/70, preferably from 90/10 to 40/60, especially from 85/15 to 50/50
  • the copolymer (C) may have a number molecular mass less than or equal to 100,000, preferably less than or equal to 70,000, most particularly from 5,000 to 60,000, measured at 100 ° C. by gel exclusion chromatography (SEC ) dissolved in dimethylacetamide (DMAC) supplemented with 10 "2 mole of LiBr; this mass is measured in polystyrene equivalent.
  • SEC gel exclusion chromatography
  • DMAC dimethylacetamide
  • Said copolymer (C) can also comprise monovalent functions other than -COOH and -NH 2 .
  • monovalent functions other than -COOH and -NH 2 By way of examples, mention may be made of hydroxy, alcohol, (R) amino, urea, imides, esters, alkyl, aryl and quaternary ammonium functions.
  • Said copolymers (C) can be of any type, linear, branched, crosslinked, etc.
  • said copolymer is a linear block polymer; the ratio number of patterns (POA) / number of patterns (PAS) is 1/2 to 2/1.
  • the optional -NH2 and -COOH monovalent functions are generally found at the ends of the copolymer chains (C).
  • Said copolymers can also comprise in their polyamide unit (s) (PAS) polyfunctional units other such as: * unsulfonated dicarbonyl units (mD) of formula -C (O) -AC (O) - , where A represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group, similar or not to the dicarbonyl sub-motif of the motif (mNS 1 ) or (mNS 3 ), not linked to a diimino-N (R) -DN (R) sub-motif ) - or to a "lactam" sub-motif -C (O) -KN (R) - * non-sulfonated multifunctional units (mP) of formula (i) -XEY- where
  • PES polyamide unit
  • the symbol E represents an aliphatic, cycloaliphatic or aromatic, polyvalent hydrocarbon group, optionally interrupted by one or more heteroatom (s) of oxygen or tertiary nitrogen, said polyvalent group being linked to at least one group X and to at least one group Y, or (ii) -C (O) -E'-C (O) - where
  • the symbol E ' represents an aliphatic, cycloaliphatic or aromatic hydrocarbon group substituted by at least one hydroxy or carboxy function
  • non-sulfonated functional units (mNS 1 ) (dicarbonyl / diimino), there may be mentioned those of which
  • the dicarbonyl sub-motif is an aliphatic or cycloaliphatic motif, the aliphatic or cycloaliphatic residue of which contains from 2 to 10 carbon atoms, such as the adipoyl, glutaroyl, succinoyl, trimethyladipoyl, pimeloyl, azeloyl, sebastreetyle, suberoyle, itaconoy, fumaroyl, dicarbonyl cyclopentanes, dicarbonyl cyclohexanes, 2-oxy methylsuccinoyl, oxymethylglutaroyl, oxyglutaroyl
  • the dicarbonyl subunit is an aromatic unit, such as the terephthaloyl, isophthaloyl, orthophthaloyl, naphthalene dicarbonyl, anthracene dicarbonyl, biphenyl dicarbonyl, oxyisophthalic dicarbonyl, 4-phthalic acid
  • the diimino sub-motif is an aliphatic motif the aliphatic residue of which is a linear, branched or cyclic alkylene group containing from 2 to 50, preferably from 2 to 20 carbon atoms and can be interrupted by one or more oxygen heteroatoms or tertiary nitrogen, like the ethylenediimino, tetramethylenediimino, hexamethylenediimino, methylpentamethylenediimino, 3-oxa-pentamethylenediimino, 3,6-dioxa-octamethylene-1,8-diimino units
  • the diimino subunit is an aromatic unit in which the aromatic residue is a phenylene radical or a bivalent radical consisting of a combination of several benzene rings optionally substituted, ortho-or peri-condensed or linked together by inert groups, such as simple valential bond, alkylene radical, oxy group, oxo group, group s
  • non-sulfonated functional units mNS 2
  • lactam non-sulfonated functional units
  • aliphatic or aromatic units including the aliphatic or aromatic contains from 2 to 20 carbon atoms, such as the 6-iminocaproyl, 11-iminoundecanoyl, 12-iminododecanoyl, 3-imino-2-dimethylpropionyl, 4- ( ⁇ -iminoethyl) benzoyl units.
  • mNS 3 ⁇ lactam'Vdicarbonyle
  • the "lactam" sub-motif is an aliphatic or aromatic motif, the aliphatic or aromatic residue of which contains from 2 to 20 carbon atoms, such as the 6-iminocaproyle, 11-iminoundecanoyl, 12-iminododecanoyl, 3-imino-2- units dimethylpropionyl, 4- ( ⁇ - iminoethyl) benzoyl * the dicarbonyl sub-motif is an aliphatic or cycloaliphatic motif of which the aliphatic or cycloaliphatic residue contains from 2 to 10 carbon atoms, such as the adipoyl, glutaroyl, succinoyl, trimethyladipoyl, pimeloyl units azeloyle, sebacoyl, suberoyl, itaconoyle, maleoyl, fumaroyl, cyclopentanes dicarbonyl cyclohexanes dicarbonyl oxy-2 procedurathylsuccin
  • non-sulfonated functional units mNS 4 ⁇ (diimino / "lactam)
  • the diimino subunit is an aliphatic unit in which the aliphatic residue is a linear, branched or cyclic alkylene group containing from 2 to 50, preferably from 2 to 20 carbon atoms and can be interrupted by one or more heteroatoms of oxygen or tertiary nitrogen, such as the ethylenediimino, tetramethylenediimino, hexamethylenediimino, methylpentamethylenediimino, 3-oxa-pentamethylenediimino, 3,6-dioxa- octamethylene-1, 8-diimino
  • the diimino sub-motif is an aromatic motif in which the aromatic residue is a phenylene radical or a bivalent radical consisting of a combination of several benzene rings optionally substituted, ortho-or peri-condensed or linked together by inert groups, such as simple valential bond, alkylene radical, oxy group, oxo group, sulfonyl group, such as the paraphenylenediimino unit, diphenylmethanediimino in which the phenyl rings are optionally substituted by a C -C 3 alkyl radical
  • the "lactam" sub-motif is an aliphatic or aromatic motif, the aliphatic or aromatic residue of which contains from 2 to 20 carbon atoms, such as the 6-iminocaproyle, 11-iminoundécanoyle, 12-iminododécanoyle, 3-imino-2- dimethylpropionyl, 4- ( ⁇ - iminoethyl) benzoyl.
  • aliphatics in which the aliphatic residue contains from 2 to 10 carbon atoms, optionally substituted by at least one aryl radical, in particular phenyl, and having at least one sulfo substituent linked to a carbon atom, such as the sulfosuccinoyl, 3-sulfoglutaroyl units, 3- (4-sulfophenyl) glutaroyl * of dicarbonyl units.
  • aromatics in which the aromatic residue is a phenylene radical or a bivalent radical consisting of a combination of several benzene rings ortho-or peri-condensed or linked together by inert groups, such as simple valential bond, alkylene radical, oxy group, oxo group, sulfonyl group, said aromatic residue having at least one sulfo substituent linked to a carbon atom, such as the sulfophthaloyl, sulfoterephthaloyl, sulfoisophthaloyl, sulfo-orthophthaloyl, sulfonaphthalenedicarbonyl, disulfo- and trisulfo-naphthalenedicarbonyl, 5- (4-sulfophenyl) units ) -isophthaloyl, 5- (2-sulfophenyl) -isophthaloyl, 5- (4-sulfophenoxy) - isophthaloyl,
  • aliphatics in which the aliphatic residue contains from 2 to 10 carbon atoms and having at least one sulfo substituent linked directly to a carbon atom, such as the 2,3-dioxypropane sulfonic, 1,5-dioxypentane-3-sulfonic units, or indirectly, as the 2,3-dioxypropane poly (oxyethylene) sulfonic units, 2,3-dioxypropane poly (oxyethylene) phenol sulfonic units, * units with oxy and carbonyl groups.
  • aliphatics in which the aliphatic residue contains from 2 to 10 carbon atoms, and having at least one sulfo substituent linked to a carbon atom, such as the 3-oxysulfopropionoyl, 5-oxy-3-sulfopentanoyl units
  • aromatics having at least one sulfo substituent linked to a carbon atom such as the sulfoparaphenylenediimino units.
  • sulfoparaphenylenediimino units such as the sulfoparaphenylenediimino units.
  • aliphatic or cvcloaliphatioues such as oxyalkyleneoxy units the alkylene residue of which is linear or branched or oxycydoalkyleneoxy, and contains from 2 to 12, preferably from 2 to 6 carbon atoms such as oxyethyleneoxy, 1,3-propanedioxy, oxypropyleneoxy, 2,2 units -propane dimethoxy, 1,4-cyclohexane dimethoxy and their higher oxy [poly (cyclo) alkyleneoxy] counterparts containing from 2 to 150 (cyclo) alkyleneoxy units, . alkane trioxy containing from 3 to 6 carbon atoms such as the units 1,2,3-propane trioxy, 1,2,4-butane trioxy and their higher poly (alkane trioxy) counterparts containing from 2 to 10 alkanetrioxy units
  • aliphatic. aromatic, heterocyclic of which the aliphatic, aromatic, heterocyclic radicals contain from 2 to 20 carbon atoms, such as the 5-iminopentanoxy-1, 4-iminomethylcyclohexanemethoxy, 5-imino-2-ethylpentanoxy, oxyisophthalic diimino units
  • the unit (PAS) preferably comprises units corresponding to aliphatic polyamides of type PA 4, PA 6, PA 10, PA 11, PA 12, PA 6.6, PA 4.6, PA 10.6 and also containing sulfonated units, preferably dicarbonyls sulfonated (sulfosuccinoyl or sulfoisophthaloye in particular), all or part of the non-sulfonated aliphatic dicarbonyl units which can be replaced by aromatic dicarbonyl units.
  • PAS preferably comprises units corresponding to aliphatic polyamides of type PA 4, PA 6, PA 10, PA 11, PA 12, PA 6.6, PA 4.6, PA 10.6 and also containing sulfonated units, preferably dicarbonyls sulfonated (sulfosuccinoyl or sulfoisophthaloye in particular), all or part of the non-sulfonated aliphatic dicarbonyl units which can be replaced by aromatic dicarbonyl units.
  • Each polyoxyalkylene unit (POA) can be linked to a sulfonated polyamide unit (PAS) via similar or different linking groups comprising at least one N, O, S heteroatom; such linking groups can be amide, ester, carbamate, oxy, ureylene, thio groups, etc.
  • the said copolymers (C) can be obtained by
  • Said sulfonated polyamide prepoplymer (PP1) can be prepared in a known manner, with monitoring the degree of progress of the polycondensation to obtain a prepolymer of desired molecular mass and preferably using an excess of diacid monomer in order to promote the formation of acid terminations.
  • polyoxyalkylene prepolymer (PP2) of which at least one end is capable of reacting with the acid and / or amino end of said prepolymer (PP1) mention may be made of those having at least one alcohol, amino, acid, epoxy, urethane end. .. , as
  • polyoxypropylene and / or polyoxyethylene diamines or triamines such as Jeffamines ® D, ED, EDR, and T marketed by Huntsman having a molecular weight in the range 1500 to 5000 .
  • polyoxyethylene and / or polyoxypropylene diepoxy having a molecular weight of the order of 300 to 5,000
  • polyoxyethylene and / or polyoxypropylene diisocyanates having a molecular weight of the order of 3000 to 5000
  • polyoxyethylene and / or polyoxypropylene dicarboxylics having a molecular weight of the order of 3000 to 5000.
  • methoxypolyoxypropylene and / or polyoxyethylenemonoamines such as
  • JEFFAMINES marketed by HUNTSMAN having a molecular mass of the order of 90 to 5,000
  • methoxypolyoxypropylene and / or polyoxyethylenemonohydroxy having a molecular weight of the order of 1000 to 25,000.
  • methoxypolyoxypropylene and / or polyoxyethylenemonoisocyanates having a molecular weight of the order of 3000 to 5000.
  • the level of SO3M functions, expressed in mass of SO3 "function, in said sulfonated polyamide prepolymer (PP1) is such that it represents at least 0.1%, preferably at least 0.2%, very particularly at least 0, 4%, especially from 0.4 to
  • the respective amounts of polymer (PP2) and (PP1) are such that the mass ratio of (PP2) / mass of (PP1) is 95/5 to 30/70, preferably 90/10 to 40/60, all particularly from 85/15 to 50/50.
  • epoxides such as epoxyalkanes containing from 4 to 18 carbon atoms - monoisocyanates, such as dodecane isocyanate
  • - quaternary acrylates or methacrylates such as MATQUAT from Atochem. They can be used in an amount such that the amount of -NH 2 functions possibly present in the final copolymer does not represent more than 80 milliequivalents per kilogram of final copolymer.
  • Said copolymer (C) can also be obtained, and this in a preferential manner, by polycondensation of the monomers (M) from which the unit is derived (PAS) in the presence of a prepolymer (PP) containing the polyoxyalkylene unit (POA) and bearing units or functions capable of condensing or reacting with at least one of said monomers, and optionally postreaction with an agent consuming amino -NH 2 functions .
  • PAS monomers from which the unit is derived
  • PP prepolymer
  • POA polyoxyalkylene unit
  • non-sulphonated dicarboxylic monomers capable of forming non-sulphonated polyfunctional units (mNS 1 ) by condensation with a diamine
  • non-sulphonated polyfunctional units mNS 3
  • lactam capable of forming non-sulphonated dicarbonyl units (mP) possible
  • aromatic dicarboxylic acids the aromatic residue of which is optionally substituted by at least one alkyl radical containing from 1 to 4 carbon atoms, a hydroxy radical, such as phthalic, terephthalic, isophthalic, orthophthalic acids, anthracene, 1, 8-naphthalene acids , 1, 4-naphthalene, biphenyl dicarboxylics, 5-hydroxy isophthalic acids, 4-hydroxy isophthalic, 4-hydroxy phthalic.
  • alkyl radical containing from 1 to 4 carbon atoms
  • a hydroxy radical such as phthalic, terephthalic, isophthalic, orthophthalic acids, anthracene, 1, 8-naphthalene acids , 1, 4-naphthalene, biphenyl dicarboxylics, 5-hydroxy isophthalic acids, 4-hydroxy isophthalic, 4-hydroxy phthalic.
  • aliphatic or cycloaliphatic dicarboxylic acids such as adipic, glutaric, succinic, trimethyladipic, pimelic, azelaic, sebacic, suberic, itaconic, maleic, fumaric acids dicarboxylic, cyclohexane dicarboxylic, 2-hydroxy-methylsuccinic, hydroxymethylglutaric, hydroxyglutaric acids.
  • non-sulphonated diamine monomers capable of forming non-sulphonated polyfunctional units (mNS 1 ) by condensation with a non-sulphonated dicarboxylic monomer, or non-sulphonated polyfunctional units (mNS 4 ) by condensation with a lactam, there may be mentioned: .
  • aliphatic diamines containing from 2 to 50 carbon atoms such as alkylenediamines, the linear, branched or cyclic alkylene group of which is optionally interrupted by one or more heteroatoms oxygen or tertiary nitrogen, such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, 3-oxa-pentamethylenediamine, 3,6-dioxa-octamethylene-1,8-diamine.
  • aromatic diamines in which the aromatic residue is a phenylene radical or a bivalent radical consisting of a combination of several benzene rings ortho-or peri-condensed or linked together by inert groups, such as simple valential bond, alkylene radical, oxy group, oxo group, sulfonyl group, such as arylenediamines such as paraphenylenediamine, diaminodiphenylmethane, the phenyl residues of which are optionally substituted by a C 2 -C 3 alkyl radical.
  • inert groups such as simple valential bond, alkylene radical, oxy group, oxo group, sulfonyl group, such as arylenediamines such as paraphenylenediamine, diaminodiphenylmethane, the phenyl residues of which are optionally substituted by a C 2 -C 3 alkyl radical.
  • non-sulphonated amino acid monomers capable of forming non-sulphonated polyfunctional units (mNS 2 ), non-sulphonated polyfunctional units (mNS 3 ) or (mNS 4 ) by condensation with a non-sulphonated dicarboxylic monomer or a non-sulphonated diamine monomer
  • MS sulfonated monomers capable of forming sulfonated polyfunctional units
  • aromatic dicarboxylic acids the aromatic residue of which is the aromatic residue is a phenylene radical or a bivalent radical consisting of a combination of several benzene nuclei ortho-or peri-condensed or linked together by inert groups, such as simple valential bond , alkylene radical, oxy group, oxo group, sulfonyl group, and is optionally substituted by at least one hydroxy substituent radical, such as sulfophthalic, sulfoterephthalic, sulfoisophthalic, sulfo-orthophthalic, 4-sulfonaphthalene-2,7 dicarboxylic acids, 5- (4-sulfophenyl) -isophthalic, 5- (2-sulfophenyl) - isophthalic, 5- (4-sulfophenoxy) -isophthalic, sulfo-bis (hydroxycarbonyl) -4,4 'diphenylsulfone
  • aliphatic dicarboxylic acids whose aliphatic residue contains from 2 to 10 carbon atoms and is optionally substituted by an aryl radical, phenyl in particular, such as sulfosuccinic acids, 3-sulfoglutaric, 3- (4-sulfophenyl) glutaric ... in acid or C ⁇ -C 4 ester form
  • sulfoaliphatic diols those having two reactive hydroxyl functions such as sulfoaliphatic diols, the aliphatic residue of which contains from 2 to 10 carbon atoms, such as 2,3-dihydroxypropanesulfonic acids, 1,5-dihydroxypentane-3-sulfonic, aliphatic diols containing 2 with 3 carbon atoms substituted by poly (oxyethylene) sulfonic or poly (oxyethylene) phenol sulfonic groups, such as the 1,2-propane diols poly (oxyethylene) sulfonic and 1,2-propane diols poly (oxyethylene) phenol sulfonic - those having a reactive hvdroxy function and a carboxy function such as aliphatic hydroxy acids, the aliphatic residue of which contains from 2 to 10 carbon atoms, such as 3-hydroxysulfopropionic, 5-hydroxy-3-sulfopentanoic acids
  • MS sulfonated monomers
  • triols containing from 2 to 20 carbon atoms such as * ethylene glycol and its higher counterparts which may contain up to 20 oxyethylene units, in particular ethylene glycol, diethylene glycol and triethylene glycol
  • linear or branched alkylene glycols which may contain up to 150 carbon atoms possibly interrupted by one or more heteroatom (s) of oxygen, such as 1,3-propanediol, propylene glycol, dipropylene glycol, 2,2 - dimethylolpropane, 1,4-cyclohexane dimethanol
  • - aliphatic hvdroxycarboxylic acids containing from 2 to 10 carbon atoms such as 3-hydroxypropionic, 4-hydroxybutyric, citric, 4-hydroxyisophthalic acid, 2,5-dihydroxytetephthalic acid
  • aliphatic, aromatic, heterocyclic amino alcohols containing from 2 to 20 carbon atoms such as 5-aminopentanol-1, 4-aminomethyl cyclohexanemethanol, 5-amino-2-ethylpentanol.
  • the monomers (M) are preferably chosen from those from which the aliphatic polyamides of the type PA 4, PA 6, PA 10, PA 11, PA 12, PA 6.6, PA 4.6, PA 10.6 are derived and also comprising sulfonated monomers, of preferably sulfonated dicarboxylic acids (sulfosuccinic or sulfoisophthalic acids in particular), all or part of the non-sulfonated aliphatic dicarboxylic acids can be replaced by aromatic dicarboxylic acids.
  • sulfonated dicarboxylic acids sulfosuccinic or sulfoisophthalic acids in particular
  • PP polyoxyalkylene chain
  • POA polyoxyalkylene chain carrying units capable of condensing or reacting with at least one of said monomers from which the sulfonated polyamide is derived
  • JEFFAMINES ® P, EP, EPR and T marketed by HUNTSMAN with a molecular weight of the order of 1500 to 5000
  • polyethylene glycols polypropylene glycols, copolymers of ethylene glycol and propylene glycol block or statistics having a molecular mass of the order of 200 to 10,000, such as PLURONICS PE from BASF
  • polyoxyethylene and / or polyoxypropylene diepoxy having a molecular weight of the order of 300 to 5,000
  • polyoxyethylene and / or polyoxypropylene diisocyanates having a molecular weight of the order of 3000 to 5000
  • polyoxyethylene and / or polyoxypropylene dicarboxylics having a molecular mass of the order of 3000 to 5000 methoxypolyoxypropylene and / or polyoxyethylenemonoamines, such as
  • JEFFAMINES ® marketed by HUNTSMAN, with a molecular weight of the order of 90 to 5,000
  • methoxypolyoxypropylene and / or polyoxyethylenemonohydroxy having a molecular weight of the order of 1000 to 25,000
  • the polycondensation operation of the monomers (M) from which the unit is derived (PAS) in the presence of said prepolymer (PP) containing the polyoxyalkylene unit (POA) can be carried out: - by bringing the prepolymer (PP) and the various monomers (M) in powder form, in liquid form, or in aqueous solution,
  • the relative amounts of the various monomers (M) being such that the molar ratio number of their carboxylic functions / number of their amino functions is at least 1, preferably at least 1.05, very particularly at least 1.1 the quantity of sulfonated monomer, expressed by mass of SO 3 , is such that it represents at least 0.1%, preferably at least 0.2%, very particularly at least 0.4%, in particular from 0.4 to 15% of the total mass of monomers (M) and prepolymer (PP) used
  • the contacting operation can be carried out at a temperature which can range from ambient temperature to 100 ° C.
  • the actual polycondensation operation can be carried out in the presence of a polyamidification catalyst; mention may in particular be made of hypophosphorous acid, phenylphosphinic acid, phenylphosphonic acid or tris (nonylphenyl) phosphite; this can be present in an amount which can range up to 1%, preferably up to 0.5% by weight relative to the total weight of prepolymer (PP) and monomers (M)
  • This operation is preferably carried out in stages
  • a step of temperature rise for example from room temperature to 280 ° C, preferably up to 270 ° C, at atmospheric pressure; this stage generally lasts from 3 to 7 hours, stage during which the water distills. a level under these same conditions, for a duration generally of the order of 10 minutes to 2 hours, preferably 1 hour
  • a postcondensation step using compounds capable of comsuming the amino -NH 2 functions can be carried out to at least partially eliminate the -NH 2 functions present.
  • - carboxylic acids such as succinic acid, sodium isophthalic acid sulfonate
  • - quaternary acrylates or methacrylates such as MATQUAT from Atochem. They can be used in an amount such that the amount of -NH 2 functions possibly present in the final copolymer does not represent more than 80 milliequivalents per kilogram of final copolymer.
  • a second object of the invention consists of a detergent for hard or textile surfaces, in particular synthetic polymer, very particularly textile surfaces of polyamide, and / or an agent capable of providing said surfaces with stain resistance properties ( stain resistance) and / or making it possible to facilitate the removal of stains and soil release from said surfaces, said agent comprising at least one of said copolymers (C) water-soluble or water-dispersible described above.
  • a third subject of the invention consists in the use of said copolymer (C) as a detergent agent for hard or textile surfaces, in particular synthetic polymer, very particularly textile surfaces in polyamide, and / or as an agent capable of providing said surfaces stain resistance properties and / or making it easier to remove stains and soil release from said surfaces.
  • a fourth object of the invention consists of a method for cleaning hard or textile surfaces, in particular synthetic polymer, very particularly polyamide textile surfaces, and / or for providing said surfaces with stain resistance properties and / or for facilitating removing stains and soiling from said surfaces, by non-permanent treatment of said surfaces using said copolymer (C) in aqueous solution or dispersion.
  • Said copolymer (C) can be used in solid formulations or aqueous liquid formulations for cleaning and / or treatment; said formulations can contain from 0.05 to 10, preferably from 0.1 to 2% by weight of copolymer (C).
  • a first embodiment consists in cleaning and / or treating hard surfaces using said copolymer (C).
  • Said hard surfaces may be ceramic, glass, porcelain, etc. Mention may be made, for example, of the use of said copolymer either as it is in aqueous solution, or within an aqueous formulation, for cleaning dishes. , bathrooms, kitchens ...
  • a particular aspect of this invention relates to aqueous shower rinsing compositions and methods for keeping the walls clean.
  • US patents US 5,536,452 and US 5,587,022 describe compositions and methods similar to those of the present invention.
  • the descriptions of US patents US 5,536,452 and US 5,587,022 are incorporated by reference in the present description.
  • the main active components of the aqueous shower rinse compositions of the present invention are at least one surfactant described below, a chelating agent of metals, and a polyamide also called below copolymer (C).
  • Preferred metal chelating agents are ethylenediaminetetraacetic acid (EPTA) and the like.
  • the aqueous shower rinse compositions typically contain water with optionally at least one lower alcohol in a large amount and each of the active constituents in lower amounts, typically said small amounts are between about 0.5% and about 3 % by weight, and even more typically between approximately 1% and approximately 2% by weight.
  • the copolymer (C) can be used in the aqueous shower wall rinse compositions in an amount of from about 0.05% to about 10% by weight, more typically from about 0.1% to about 2% by weight of the aqueous composition for rinsing showers.
  • compositions can be applied by spraying onto the surface of the shower walls, after moistening said walls with water.
  • a second embodiment consists in cleaning and / or treating textile surfaces using said copolymer (C).
  • the textile surfaces are made of a synthetic organic polymer, in particular of polyamide; especially these are surfaces textiles such as rugs, carpets, fabrics, clothing, underwear, furniture, sporting goods, etc., made of synthetic organic polymer, in particular polyamide.
  • Said copolymer (C) makes it possible to provide these textile surfaces with hydrophilic properties, resistance to stains, in particular to greasy (polish, ballpoint pen, lipstick, oil, etc.) or aqueous (coffee, etc.) stains. .).
  • Said copolymers (C) or the compositions or formulations comprising said copolymers (C), placed in aqueous solution or dispersion (before or during treatment), can be deposited on textile surfaces by pouring with possible friction, by spraying, by application to using an appliance, by washing and / or rinsing and / or softening by hand or in the machine. They can also, after impregnation of a support made of a cellulosic material for example, be deposited by contact in a device for drying said textile surfaces.
  • One particular aspect relates to solid or liquid compositions for washing and / or rinsing and / or softening of linen or clothing by hand or in the machine.
  • the copolymer (C) makes it possible to add hydrophilicity to the linen or to the clothes, which results in a better permeability of the synthetic textile to water vapor and thus a better comfort in contact with the skin.
  • compositions for washing and / or rinsing and / or softening linen or clothes can contain from 0.05 to 10, preferably from 0.1 to 2% by weight of copolymer (C).
  • the washing compositions may further comprise - anionic surfactants such as
  • the alkyl esters sulfonates of formula R-CH (S ⁇ 3M) -COOR ' where R represents an alkyl radical in Cs-20' preferably in C10-C16 ' ⁇ ' an alkyl radical in C-
  • alkyl sulfates of formula ROSO3M where R represents a C5-C24, preferably C-
  • M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated derivatives (OE) and / or propoxylenes (OP), having on average from 0.5 to 30 units, preferably from 0, 5 to 10 OE and / or OP motifs;
  • alkylamide sulfates of formula RCONHROSO3M where R represents a C2-C22 alkyl radical. preferably O3-C20.
  • R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated derivatives (OE) and / or propoxylenes (OP), having on average from 0.5 to 60 OE and / or OP units;
  • polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units oxyethylene, oxypropylene
  • TERGITOL 15-S-9 TERGITOL 24-L-6 NMW sold by Union Carbide Corp.
  • NEOPOL 45-9 NEOPOL 23-65, NEOPOL 45-7
  • NEOPOL 45-4 marketed by Shell Chemical Cy
  • KYRO EOB marketed by The Procter & Gamble Cy
  • SYNPERONIC A3 to A9 from ICI
  • ethoxylated amines containing from 5 to 30 ethoxylated units; . alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, more particularly from 2 to 20 oxyalkylene units (preferably oxyethylene;. amine oxides such as alkyl oxides C-
  • alkylpolyglycosides obtainable by condensation (for example by acid catalysis) of glucose with primary fatty alcohols (US-A-3,598,865; US-A-4,565,647; EP-A-1 32,043; EP-A- 132 046 ...) having a C4-C2O 'alkyl group, preferably Cs-Ci s * a i ns ⁇ that an average number of glucose units of the order of 0.5 to 3, preferably of the order from 1.1 to 1.8 per mole of alkylpolyglycoside (APG); we can mention in particular those presenting
  • GLUCOPON 600 EC® an alkyl group in CS-C -JQ and on average 1, 6 glucose unit per mole sold respectively under the names GLUCOPON 600 EC®, GLUCOPON 600 CSUP®, GLUCOPON 650 EC®, GLUCOPON 225 CSUP®, by HENKEL and / or with amphoteric and zwitterionic surfactants.
  • alkyl betaines such as alkyl betaines, alkyldimethyl betaines, alkylamidopropyl betaines, alkylamidopropyldimethyl betaines, alkyltrimethyl sulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylamphopropionates, alkyl-amphodi-propionates, alkyl-amphodipropionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, alkyl-amphodi-propionates, al
  • surfactants being used in an amount of the order of 5 to 70%, preferably 5 to 50% of the weight of said composition; detergency builders (mineral or organic builders), in an amount such that the total amount of detergency builder is of the order of 5 to 80% of the weight of said composition, detergency builders such as
  • - polyphosphates tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates of alkali metals, ammonium or alkanolamines
  • alkali metal silicates - alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates) - alkali metal silicates
  • - aminophosphonates such as nitrilotris (methylene phosphonates) other anti-fouling agents, in amounts of the order of 0.01-10%, preferably of the order of 0.1 to 5%, and very particularly of 0.2-3% by weight, agents such as - cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose
  • terephthalic copolyester oligomers containing sulfoisophthaloyl units in their chain of anti redeposition agents in amounts of about 0.01-10% by weight for a powdered detergent composition, about 0.01-5% by weight for a composition liquid detergent, agents such as
  • the water-soluble salts of carboxylic polymers or copolymers such as the polyacrylic acid salts, the copolymers of acrylic acid and maleic anhydride of bleaching agents, in an amount of about 0.1-20%, preferably 1- 10% of the weight of said powdered detergent composition, such as
  • peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, failed urea peroxyhyd, sodium peroxide, sodium persulfate - percarboxylic acids and their salts (called "percarbonates") preferably associated with an activator bleaching generating, in situ in the washing medium, a peroxycarboxylic acid; among these activators, mention may be made of tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose, etc. foam suppressants, in amounts up to 5% by weight, agents such as
  • silica particles, softening agents in amounts of about 0.5-10% by weight, agents such as clays of enzymes in amounts up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as proteases, amylases, lipases, peroxidases, cellulase, color transfer inhibitory agents, fluorescence agents and other additives such as
  • - buffering agents or fillers such as sodium sulphate, carbonates or bicarbonates of alkaline earth metals.
  • the rinsing and / or softening compositions may comprise, alongside the copolymer (C) at least one cationic surfactant in an amount which can range from 5 to 70%, optionally at least one nonionic surfactant in an amount which can range up to 10% , optical brighteners, dyes, perfumes, sequestrants
  • compositions are preferably liquid.
  • a last particular aspect consists in cleaning and / or treating carpets or rugs.
  • the copolymer (C) in aqueous solution or dispersion can be used very particularly in the formulations for carpets or rugs, as detergent agent, and / or as agent bringing resistance to stains and / or as agent facilitating the removal of stains. It can be deposited on said surface to be treated by spraying, by application using a shampooer, using an injection-extraction device of the solution comprising said copolymer, or by simply pouring the solution of copolymer on the surface to be treated, with possible friction using a sponge or a brush.
  • Said formulations can contain from 0.1 to 10, preferably from 0.1 to 2% by weight of copolymer (C). Said formulations can optionally be diluted before use.
  • Said copolymer (C) can be used in quantities, expressed as dry matter of the order of 0.01 to 5, preferably from 0.05 to 3 g / m 2 of surface.
  • Said composition may also comprise other additives such as anionic, and / or nonionic and / or amphoteric or zwitterionic surfactants in an amount which can range from 0.1 to 20%, detergency builders ("builders ”) in an amount which can range from 0.5 to 10%, acrylic polymers in a quantity which can range from 0.1 to 10%, anti-fouling agents, anti-deposition agents, perfumes ...
  • additives can be of the same type than those already mentioned above. It can also include alcoholic solvents and bleaching agents such as hydrogen peroxide.
  • the present invention also relates to solid or liquid detergent compositions comprising said copolymer (C).
  • Adipic acid is added in an amount necessary to reach the point of neutralization of the solution (here 1.332 g, ie 9.12 mmol); the solution is still left stirring for 24 hours. When the dissolution is complete, two samples are again taken. A stoichiometric solution is obtained, of the following weight composition: Jeffamine EP 2003: 46.88% by weight
  • Adipic acid 3.18% by weight water: 49.94% by weight
  • AISNa 5.39% by weight water: 49.97% by weight
  • reaction mass is returned to atmospheric pressure and then cooled. It is then extracted from the reactor.
  • the copolymer is analyzed in terms of terminal groups (NH2 and COOH) and of molecular mass.
  • the content of NH2 groups having been measured, the quantity of anhydride to be added is calculated by considering that an NH2 function reacts with an anhydride cycle.
  • reaction mass is brought to 200 ° C. under vacuum for 2 hours.
  • reaction mass is returned to atmospheric pressure and then cooled.
  • the copolymer is analyzed in terms of terminal groups (NH2 and COOH).
  • Adipic acid is added in an amount necessary to reach the point of neutralization of the solution (here 1.332 g, ie 9.12 mmol); the solution is still left stirring for 24 hours. When the dissolution is complete, two samples are again taken. A stoichiometric solution is obtained, with the following weight composition:
  • Adipic acid 3.18% by weight water: 49.94% by weight
  • the copolymer is analyzed in terms of terminal groups (NH2 and COOH) and of molecular mass.
  • the content of NH2 groups having been measured, the quantity of anhydride to be added is calculated by considering that an NH2 function reacts with an anhydride cycle.
  • reaction mass is returned to atmospheric pressure and then cooled.
  • the copolymer is analyzed in terms of terminal groups (NH2 and COOH).
  • Adipic acid is added in an amount necessary to reach the neutralization point of the solution (here 0.536 g or 3.67 mmol); the solution is still left stirring for 24 hours. When the dissolution is complete, two samples are again taken. A stoichiometric solution is obtained, of the following weight composition: Jeffamine EP 2003: 46.986% by weight
  • Adipic acid 3.046% by weight water: 49.968% by weight
  • AISNa 5.335% by weight water: 50% by weight
  • the temperature thus reaches 260 ° C in 3 hours during which water distills. A bearing at atmospheric pressure for one hour and then another at reduced pressure for 2 hours are applied. After these stages, the reaction mass is returned to atmospheric pressure and then cooled. It is then extracted from the reactor.
  • the copolymer is analyzed in terms of terminal groups (NH2 and COOH) and of molecular mass.
  • reaction mass is brought under vacuum to 200 ° C for 1 hour, then to 250 ° C for 2 hours.
  • reaction mass is returned to atmospheric pressure and then cooled.
  • the copolymer is analyzed in terms of terminal groups (NH2 and COOH).
  • copolymers of Examples 1 to 3 are tested for their hydrophilization properties, stain resistance agent and agent for facilitating the removal of stains.
  • a film of Polyamide PA 6.6 having a surface of 70 cm 2 is introduced into an ethanol bath and cleaned at room temperature under ultrasound for 30 minutes, then rinsed with demineralized water and heated for 2 hours in demineralized water boiling, in order to remove any traces of oligomers from the film.
  • the conditioned film thus obtained is immersed at room temperature in a volume of 200 ml of an aqueous solution containing 2.5 g / l of copolymer to be tested, for 2 hours with stirring, then rinsed twice for 10 minutes with water. demineralized with stirring, and left to dry in air at a relative humidity of 80% for 7 days.
  • This protocol makes it possible to obtain a reproducible film surface and adsorption. Only any copolymer chains in direct interaction with the PA film are left on the surface.
  • control surface is produced by following the same protocol but by immersing the PA film in a solution of demineralized water containing no polymer.
  • control surface will therefore be understood below as meaning the PA film free of its oligomers, then immersed in demineralized water and left to dry.
  • the PA film tested was treated with the copolymer 3.4 of Example 3.
  • the surface properties of the treated film are determined by wetting measurement in double liquid geometry.
  • a drop of demineralized water (volume 1 ⁇ l) is deposited on the surface of the support.
  • the angle at equilibrium ⁇ which characterizes the wetting is governed by the surface energy of the substrate and the surface tensions of the liquids present; it is measured after 20 minutes. The greater the hydrophilization provided by the copolymer, the lower ⁇ .
  • the results obtained are as follows
  • a film of Polyamide PA 6.6 having an area of 50 cm 2 is introduced into an ethanol bath and cleaned at room temperature under ultrasound for 30 minutes, then rinsed with demineralized water and heated for 2 hours in boiling demineralized water, in order to remove any traces of oligomers from the film.
  • the conditioned film thus obtained is immersed at room temperature in a volume of 250 ml of an aqueous solution containing 2.5 g / l of copolymer to be tested, for 2 hours with stirring, then rinsed twice for 10 minutes with water. demineralized with stirring, and left to air dry at a relative humidity of 80% for 7 days.
  • This protocol makes it possible to obtain a reproducible film surface and adsorption. Only any copolymer chains in direct interaction with the PA film are left on the surface.
  • control surface is produced by following the same protocol but by immersing the PA film in a solution of demineralized water containing no polymer.
  • control surface will therefore be understood below as meaning the PA film free of its oligomers, then immersed in demineralized water and left to dry. Coffee staining test (stain resistance - "stain resistance” -)
  • the PA film (50 cm 2 ) tested was treated as described above in a volume of 250 ml of 2.5 g / l solution of the copolymers 1.3, 1.4, 2.3, 2.4, 3.3 and 3.4 of Examples 1 to
  • the aqueous solutions of treatment copolymer are applied to pieces of Sommer beige tufted carpet (reference New Neptune color J480, 100% polyamide pile, 1840 g / m 2 ) by spraying, so as to obtain a deposit of copolymer (expressed in dry) of 0.05, 0.1 or 0.5 part by weight per 100 parts by weight of pile.
  • 100 ml of copolymer solution are sprayed per 100 g of pile, the surface mass of the "useful" carpet (pile) is evaluated at 600 g / m 2 .
  • An untreated piece of carpet serves as a witness.
  • the method consists in carrying out various stains on the carpet pieces treated with a solution of copolymer 3.4 and in carrying out their stain removal with the cleaning product according to the instructions given by the supplier.
  • the carpet pieces are stained with the following 4 staining products:
  • Foam cubes are fouled, in a rotary stoneware agitator, with a suspension of dust standardized in perchorethylene.
  • the samples are fouled by fixing them to the inner wall of a cylindrical barrel which is rotated and in which the soiled and dried foam cubes, porcelain balls and a tetrapod have been placed. These soiled samples are photometric.
  • Soiled samples are vacuumed using a vacuum cleaner provided for this purpose.
  • the injection-extraction of the pretreated samples is carried out by fixing them in the three cells of a plate provided for this purpose, and using an injection-extraction machine with a solution of the cleaning product.
  • the samples are then dried in the open air, then aspirated and photometric.
  • the carpet is cut into 4 "x4" squares (approximately 10x10cm 2 ) which are marked below to ensure that all the pile is oriented in the same direction from one square to another to obtain characteristics of similar appearance (less reflection).
  • the oil stains are produced using the micro-pipette; the waxy stains are first weighed on the application sponge and then applied to the carpet samples.
  • the oil stains are applied at a dose of 0.12 ⁇ 0.05g for each carpet sample inside a 2 "x2" square mask (approximately 5x5 cm 2 ) using a spatula.
  • the waxes are applied at a weight dose of 0.15 ⁇ 0.05 g.
  • the samples are dried four times (each time for 5 seconds), using white paper towels.
  • the soil removal R is calculated as follows:

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EP00910901A 1999-03-09 2000-03-03 Sulfoniertes copolymer und verfahren zur reinigung von oberflächen und/oder zur herstellung von flecken abweisenden eigenschaften dieser oberflächen und/oder zur entfernung von flecken oder verschmutzungen Expired - Lifetime EP1161516B1 (de)

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PCT/FR2000/000537 WO2000053711A1 (fr) 1999-03-09 2000-03-03 Copolymere sulfone et procede pour nettoyer les surfaces et/ou apporter a celles-ci des proprietes de resistance aux taches et/ou faciliter l'enlevement des taches et de la salissure

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FR2837205B1 (fr) * 2002-03-15 2005-05-06 Rhodia Chimie Sa Copolyesteramides et leur utilisation comme agent antisalissure
US7892993B2 (en) 2003-06-19 2011-02-22 Eastman Chemical Company Water-dispersible and multicomponent fibers from sulfopolyesters
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WO2000053711A1 (fr) 2000-09-14
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